Froth flotation is one of the most widely used processes for beneficiating ores containing valuable minerals. It is especially useful for separating finely ground valuable minerals from their associated gangue or for separating valuable minerals from one another. The process is based on the affinity of suitably prepared mineral surfaces for air bubbles. In froth flotation, a froth or a foam is formed by introducing air into an agitated pulp of the finely ground ore in water containing a frothing or foaming agent. A main advantage of separation by froth flotation is that it is a relatively efficient operation at a substantially lower cost than many other processes.
It is common practice to include in the flotation process, one or more reagents called collectors or promoters that impart selective hydrophobicity to the valuable mineral that is to be separated from the other minerals. It has been suggested that the flotation separation of one mineral species from another depends upon the relative wettability of mineral surfaces by water. Many types of compounds have been suggested and used as collectors in froth flotation processes for the recovery of metal values. Examples of such types of collectors include the xanthates, xanthate esters, dithiophosphates, dithiocarbamates, trithiocarbonates, mercaptans and thionocarbonates. Xanthates and dithiophosphates have been employed extensively as sulfide collectors in froth flotation of base metal sulfide ores.
Dialkyldithiophosphoric acids and salts thereof such as the sodium, potassium or ammonium salts have been utilized as promoters or collectors in the beneficiation of mineral-bearing ores by flotation for many years. Early references to these compounds and their use as flotation promoters may be found in, for example, U.S. Pat. Nos. 1,593,232 and 2,038,400. Ammonium salt solutions of the dithiophosphoric acids are disclosed as useful in U.S. Pat. No. 2,206,284, and hydrolyzed compounds are disclosed as useful in U.S. Pat. No. 2,919,025.
The dialkyldithiophosphoric acids utilized as flotation promoters and collectors for sulfide and precious metal ores are obtained by reacting an alcohol with phosphorus and sulfur generally as P.sub.2 S.sub.5. The acid obtained in this manner can then be neutralized to form a salt.
U.S. Pat. No. 3,086,653 describes aqueous solutions of alkali and alkaline earth metal salts of phospho-organic compounds useful as promoters or collectors in froth flotation of sulfide ores. The phospho-organic compounds are neutralized P.sub.2 S.sub.5 -alkanol reaction products. Although single alcohols are normally used in the reaction, the patentees disclose that mixtures of isomers of the same alcohol, and mixtures of different alcohols may be utilized as starting materials in the preparation of the phosphorus compound, and the resulting acidic products can be readily neutralized to form stable solutions which are useful as flotation agents.
U.S. Pat. No. 3,570,772 describes the use of di(4,5-carbon branched primary alkyl) dithiophosphate promoters for the flotation of copper middlings. The 4 and 5 carbon alcohols used as starting materials may be either single alcohols or mixtures of alcohols.
U.S. Pat. No. 3,298,520 issued to Bikales relates to the use of 2-cyanovinyldithiocarbamates which are useful as promotors in benefication of ores by froth flotation.
U.S. Pat. No. 4,372,864 issued to McCarthy relates to a reagent which is useful in the recovery of bituminous coal in froth flotation processes. The reagent of the invention comprises a liquid hydrocarbon, a reducing material and an activator material. The reducing material is phosphorus pentasulfide and the activator material is zinc ethylene bis(dithiocarbamate).
U.S. Pat. Nos. 4,514,293 issued to Bresson et al and 4,554,108 issued to Kimble et al relate to the use of N-carboxyalkyl-S-carboalkoxydithiocarbamates and carboxyalkyldithiocarbamates, respectively, as ore flotation reagents.
U.S. Pat. No. 4,595,538 issued to Kimble et al relates to the use of trialkali metal or triammonium N,N-bis(carboxyalkyl)dithiocarbamates as ore flotation depressants.
U.S. Pat. No. 3,876,550 issued to Holubec relates to lubricant compositions containing an additive combination which comprises (A) an alkylene dithiocarbamate and (B) a rust inhibitor based on a hydrocarbon-substituted succinic acid or certain derivatives thereof.
U.S. Pat. Nos. 1,726,647 and 1,736,429 issued to Cadwell relate to phenylmethylene bisdithiocarbamates and methods for preparing the same.
U.S. Pat. Nos. 4,040,950 issued to Zeparian, 4,584,097 issued to Fu et al, and 4,699,712 issued to Unger relate to a mixture of a dithiophosphorus acid or salt with a thionocarbamate in an ore flotation process.
U.S. Pat. No. 4,879,022 issued to Clark et al relates to dithiophosphorus acid or salt used in a flotation process utilizing sulfurous acid. Thionocarbamate is disclosed as an auxilliary collector.
Procedures for the selective flotation of copper minerals from copper sulfide ores wherein a slurry of ore and water is prepared and sulfurous acid is added to the slurry to condition the slurry prior to the froth flotation step have been discussed in, for example, U.S. Pat. Nos. 4,283,017 and 4,460,459. Generally, the pulp is conditioned with sulfur dioxide as sulfurous acid under intense aeration.